WO2006093156A1 - Composition de revetement et article revetu - Google Patents

Composition de revetement et article revetu Download PDF

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Publication number
WO2006093156A1
WO2006093156A1 PCT/JP2006/303767 JP2006303767W WO2006093156A1 WO 2006093156 A1 WO2006093156 A1 WO 2006093156A1 JP 2006303767 W JP2006303767 W JP 2006303767W WO 2006093156 A1 WO2006093156 A1 WO 2006093156A1
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Prior art keywords
group
coating
material composition
coating material
sio
Prior art date
Application number
PCT/JP2006/303767
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English (en)
Japanese (ja)
Inventor
Akira Tsujimoto
Ryozo Fukuzaki
Takeyuki Yamaki
Hiroshi Yokogawa
Original Assignee
Matsushita Electric Works, Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Application filed by Matsushita Electric Works, Ltd. filed Critical Matsushita Electric Works, Ltd.
Priority to JP2007505961A priority Critical patent/JPWO2006093156A1/ja
Priority to EP06714896A priority patent/EP1854854A4/fr
Priority to US11/816,832 priority patent/US8273811B2/en
Publication of WO2006093156A1 publication Critical patent/WO2006093156A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
    • C08G59/306—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • C08G77/50—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/14—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance
    • C09D5/1675—Polyorganosiloxane-containing compositions
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/18—Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films

Definitions

  • the present invention relates to a coating material composition having a low refractive index and capable of realizing high scratch resistance, antifouling properties, chemical resistance, and crack resistance, and a coated product formed with a cured film thereof.
  • hydrolyzable silane compounds having a perfluoroalkyl group have been developed, and various coating agents such as water repellency, oil repellency, antifouling property, and antireflection property have been developed by making use of the characteristics.
  • various coating agents such as water repellency, oil repellency, antifouling property, and antireflection property have been developed by making use of the characteristics.
  • the perfluoroalkyl groups that provide these properties are bulky and inert, which reduces the crosslink density of the cured film, and as a result, is considerably harder than fluorinated resin, but it is scratch resistant. Sex is still inadequate.
  • composition disclosed in Japanese Patent Application Laid-Open No. 2004-315712 contains a disilane compound having a specific structure or a (partial) hydrolyzate thereof, thereby providing a higher level than before. Has achieved chemical resistance.
  • a disilane compound having a specific structure or a (partial) hydrolyzate thereof thereby providing a higher level than before. Has achieved chemical resistance.
  • the present invention has been made in view of the above points. Even when a film is formed on a plastic base material such as a plastic substrate, the present invention is performed at a high temperature during the film formation or after the film formation.
  • a coating material composition that can maintain high scratch resistance, antifouling properties, chemical resistance, and crack resistance when exposed to light, and a film formed from the coating material composition The purpose is to provide a painted product.
  • the coating material composition according to the present invention comprises a silanic compound represented by the following general formula (A) and an epoxy group-containing organic compound containing one or more epoxy groups in the molecule,
  • the content of the silane compound is 60 to 97% by weight with respect to the total amount of the resin component, and the content of the epoxy group-containing organic compound is 3 to 10% by weight with respect to the total amount of the resin component. It is a feature.
  • R 1 is a monovalent hydrocarbon group having 1 to 6 carbon atoms.
  • Y is a divalent organic group containing one or more fluorine atoms.
  • X is a hydrolyzable group.
  • m is an integer of 1 to 3.
  • a film formed of such a coating material composition can maintain high crack resistance even when exposed to high temperatures.
  • the epoxy group-containing organic compound contains at least one compound selected from a compound represented by the following general formula (B) and a compound represented by the following general formula (C). Is preferred. [0014] R 2 R 3 SiZ (B)
  • R 2 and R 3 are organic groups having 1 to 16 carbon atoms, and at least one of them contains an epoxy group.
  • Z is a hydrolyzable group.
  • n and p are integers between 0 and 2, l ⁇ n + p ⁇ 3.
  • R 4 to R 15 are organic groups, and at least one of them contains an epoxy group.
  • q, r, s, and t are integers from 0 to 12.
  • the epoxy group-containing organic compound preferably contains two or more epoxy groups in the molecule! /.
  • the coating material composition preferably contains a fluorinated alkyl group-containing alkoxysilane represented by the following general formula (D).
  • R is a monovalent organic group containing one or more fluorine atoms.
  • X is a hydrolyzable group.
  • the said coating material composition contains a filler.
  • the content of the epoxy group-containing organic compound is preferably 3 to 10% by weight based on the silane compound represented by the general formula (A).
  • the coated product according to the present invention is characterized in that a cured film of the coating material composition as described above is formed on the surface of a substrate.
  • a coating material composition according to the present invention comprises a silanic compound represented by the following general formula (A):
  • an organic compound containing an epoxy group containing at least one epoxy group in the molecule as an essential component.
  • R 1 is a monovalent hydrocarbon group having 1 to 6 carbon atoms.
  • Y is divalent and contains one or more fluorine atoms Mechanism.
  • X is a hydrolyzable group.
  • m is an integer of 1 to 3.
  • Y in the formula (A) is a divalent organic group having one or more fluorine atoms, and the number of fluorine atoms is preferably 4 to 50, particularly preferably 8 to 24.
  • the perfluoroalkylene group is rigid, it is preferable that it contains as many fluorine atoms as possible for the purpose of obtaining a film having high hardness and high scratch resistance. If it contains a large amount of fluorine atoms, chemical resistance will be improved. Therefore, Y preferably has the following structure.
  • N in the above structure is a force that needs to satisfy a value of 2 to 20, more preferably 4 to 12, and particularly preferably 4 to 10. If it is less than this, it may not be possible to sufficiently obtain various functions such as antireflection properties, antifouling properties and water repellency, and chemical resistance. Is not possible!
  • R 1 represents a monovalent hydrocarbon group having 1 to 6 carbon atoms.
  • alkyl such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and a cyclohexyl group Examples thereof include a group and a phenol group.
  • a methyl group is preferred for obtaining good scratch resistance.
  • X represents a hydrolyzable group. Specific examples include halogen atoms such as C1, OR (R is
  • Monooxy hydrocarbon groups having 1 to 6 carbon atoms especially alkoxy groups such as methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, alkenoxy groups such as isopropenoxy group, and acetooxy group.
  • alkoxy groups such as methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, alkenoxy groups such as isopropenoxy group, and acetooxy group.
  • alkoxy groups such as methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, alkenoxy groups such as isopropenoxy group, and acetooxy group.
  • alkoxy groups such as methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, alkenoxy groups such as isopropenoxy group, and acetooxy group.
  • alkoxy groups such as methoxy group, ethoxy group, propoxy group, isopropoxy group, but
  • the silanic compound represented by the general formula (A) in the coating material composition is in the range of 60 to 97% by weight, preferably 65 to 85% by weight, based on the total amount of the resin components. It is included in the range. Therefore, it is possible to improve the chemical resistance of the coating by the silane compound represented by the general formula (A), and to improve the alkali resistance, which has been a problem of the conventional polysiloxane coating. It can be done.
  • an epoxy group-containing organic compound containing one or more epoxy groups in the molecule an appropriate one can be used, particularly one containing two or more epoxy groups in the molecule.
  • the chemical resistance of the coating can be further improved.
  • Such an epoxy group-containing organic compound containing two or more epoxy groups in the molecule is contained in a range of 3 to 10% by weight based on the total amount of the resin component. If it is less than 3% by weight, the crack resistance of the film cannot be sufficiently improved, and if it is more than 10% by weight, the chemical resistance of the film cannot be sufficiently improved, and the wear resistance of the film is not improved. May decrease.
  • the epoxy group-containing organic compound one selected from a compound represented by the following general formula (B) and a compound represented by the following general formula (C) is preferably used.
  • One or more kinds of such compound powers can be used.
  • the crack resistance can be further improved without reducing the chemical resistance and wear resistance of the coating.
  • the total content of this epoxy group-containing organic compound is 3 to 10 wt. If the content is too small, the crack resistance may not be sufficiently improved, and if the content is excessive, chemical resistance and resistance Abrasion may be reduced.
  • R 2 and R 3 are organic groups having 1 to 16 carbon atoms, and at least one of them contains an epoxy group.
  • ⁇ is a hydrolyzable group.
  • ⁇ and ⁇ are integers from 0 to 2, and 1 ⁇ + ⁇ 3.
  • R 4 to R 15 are organic groups, and at least one of them contains an epoxy group.
  • q, r, s, and t are integers from 0 to 12.
  • the compound represented by the general formula (B) is appropriately selected depending on the purpose such as adhesion to the substrate, hardness and low reflectivity of the resulting coating film, and the life of the composition. .
  • R 4 to R 15 in the formula may include an organic group such as an appropriate hydrocarbon group such as a methyl group. Further, at least one of R 4 to R 15 contains an epoxy group, and examples thereof include those having the following structure.
  • [POA is a polyether group, preferably one C 3 H 6 0 (C 2 H 4 0) a (C 3 H 6 0) b R ′ &, 1) is an integer of 0 to 12.
  • R ′ is a hydrocarbon group] H 2
  • epoxy group-containing organic compound in addition to those represented by the general formulas (B) and (C), an appropriate epoxy compound can be used. Examples of such epoxy compounds include those shown below.
  • the content of the epoxy group-containing organic compound is appropriately adjusted, but preferably 3 to 10% by weight with respect to the silane compound represented by the general formula (A). By doing so, the crack resistance without lowering the chemical resistance and wear resistance of the coating can be further improved. If this content is less than the above range, it is difficult to sufficiently improve the crack resistance, and if it exceeds this range, the chemical resistance and the wear resistance may be lowered.
  • the coating material composition may contain a fluoroalkyl group-containing alkoxysilane represented by the following general formula (D).
  • [R contains one or more fluorine atoms
  • X is a hydrolyzable group. When such a material is contained, the refractive index of the formed film can be further reduced.
  • the number of fluorine atoms in Rf is preferably 3 to 25, particularly 3 to 17.
  • X as the hydrolyzable group may be the same as that in the general formula (A).
  • Examples of the fluorinated alkyl group-containing alkoxysilane represented by the general formula (D) include the following.
  • the content of the fluorinated alkyl group-containing alkoxysilane represented by the general formula (D) and its hydrolyzate (partially hydrolyzate) are adjusted as appropriate, but the scratch resistance of the coating decreases as the amount added increases. Therefore, the range of 1 to 30% by weight with respect to the total amount of the fat component in the composition It is preferable that 1 to 10% by weight is particularly preferable.
  • the coating agent composition includes silica, acid aluminum, titanium oxide, zinc oxide, acid as a filler for the purpose of adjusting physical properties such as film hardness, scratch resistance, and conductivity.
  • Inorganic fine particles such as zirconium, cerium oxide, tin oxide, indium oxide, or composite oxides thereof, or a hollow sol thereof may be blended.
  • colloidal silica and hollow silica sol are preferably used in order to maintain the coating film at a low refractive index.
  • the preferred inorganic fine particles preferably have an average primary particle diameter of 0.001-0. 1 m, more preferably 0.001-0.05 / z m.
  • the transparency of the cured film formed by the prepared composition tends to decrease.
  • these inorganic oxide fine particles those whose surface is treated with an organometallic compound such as a silanic, titanium, aluminum or zirconium coupling agent may be used.
  • hollow fine particles whose outer shell is formed of a metal oxide can also be blended.
  • hollow silica fine particles can be used.
  • the hollow silica fine particles are those in which cavities are formed inside the outer shell, and are not particularly limited as long as they are such, but specifically, the following can be used.
  • Silica-based inorganic oxides are: (A) a single layer of silica, (B) a single layer of a composite oxide consisting of silica and an inorganic oxide other than silica, and (C) the above (A) This includes a double layer of the layer and the (B) layer.
  • the outer shell may be porous having pores, or may be one in which the pores are closed by an operation described later and the cavity is sealed.
  • the outer shell is preferably a plurality of silica-based coating layers composed of an inner first silica coating layer and an outer second silica coating layer. By providing the second silica coating layer on the outside, the fine pores of the outer shell are closed to make the outer shell dense, and furthermore, hollow silica fine particles in which the inner cavity is sealed with the outer shell can be obtained. It is.
  • the thickness of the first silica coating layer is preferably in the range of 1 to 50 nm, particularly 5 to 20 nm. If the thickness of the first silica coating layer is less than 1 nm, it may be difficult to maintain the particle shape, and hollow silica fine particles may not be obtained. When forming, the partial hydrolyzate of the organosilicon compound may enter the pores of the core particles, which may make it difficult to remove the core particle constituents. On the contrary, if the thickness of the first silica coating layer exceeds 50 nm, the ratio of the cavities in the hollow silica fine particles may be reduced, and the refractive index may not be sufficiently lowered.
  • the thickness of the outer shell is preferably in the range of 1Z50 to LZ5 of the average particle diameter.
  • the thickness of the second silica coating layer should be such that the total thickness with the first silica coating layer is in the range of 1 to 50 nm, particularly in the case of densifying the outer shell, the range of 20 to 49 nm. Is preferred.
  • a precursor material for forming the cavity may remain in the cavity.
  • the precursor material may remain slightly attached to the outer shell or may occupy most of the cavity.
  • the precursor substance is a porous substance that remains after the nuclear particle force for forming the first silica coating layer also removes some of its constituent components.
  • porous composite oxide particles composed of silica and inorganic oxides other than silica are used. Inorganic oxides include Al O, B 2 O, TiO
  • Two or more inorganic oxides such as TiO-AlO, TiO-ZrO, etc.
  • the solvent or gas is also present in the pores of the porous material.
  • the transparent film obtained by blending the hollow silica fine particles reflects with a low refractive index. Excellent prevention performance.
  • the coating material composition according to the present invention can be prepared by blending the matrix-forming material and hollow fine particles.
  • silica particles can be added to the coating material composition in which the inside of the outer shell is not hollow.
  • the form of the silica particles is not particularly limited, and may be, for example, a powder form or a sol form.
  • a sol form that is, as colloidal silica
  • water-dispersible colloidal silica or alcohol-dispersible colloidal in a hydrophilic organic solvent should be used.
  • colloidal silica contains 20 to 50% by mass of silica as a solid content, and this value can also determine the amount of silica.
  • the addition amount of the silica particles is preferably 0.1 to 30% by mass with respect to the total solid content in the coating material composition. If the amount is less than 0.1% by mass, the effect of adding silica particles may not be obtained. Conversely, if the amount exceeds 30% by mass, the refractive index of the cured film may be adversely affected.
  • the filler When the filler is contained as described above, it is possible to further improve the wear resistance of the coating film, and in particular, low refractive index filling such as magnesium fluoride or hollow particles having a low refractive index. If the material is added, the refractive index can be expected to be further reduced.
  • organosilicon compounds that can be used in combination include dialkylsiloxy hydrolyzable organosilanes represented by the following general formula.
  • R 1 , R 2 , R is an alkyl group, m is an integer of 1 to 3, and n is an integer of 2 to 200]
  • organosilicon compounds include silicates such as tetraethoxysilane, alkylsilanes such as methyltrimethoxysilane, hexyltrimethoxysilane, decyltrimethoxysilane, and the like.
  • silicates such as tetraethoxysilane, alkylsilanes such as methyltrimethoxysilane, hexyltrimethoxysilane, decyltrimethoxysilane, and the like.
  • Rushiran acids, ⁇ - - Hue such Le trimethoxysilane ⁇ amino propyl triethoxy silane, .gamma.-methacryloxypropyl trimethoxysilane, .gamma.-mercaptopropyl various I ⁇ of silane coupling agents such as trimethoxysilane Can be mentioned.
  • organosilicon compounds are preferably 30% by weight or less based on the total amount of the resin component. If the content is excessive, the crack resistance of the film may be lowered, or the hydrophilicity may be increased and the chemical resistance may be lowered.
  • the compounds represented by the above formulas (A), ( ⁇ ), (D), or other organosilicon compounds that can be used in combination may be used as they are, or (partially) hydrolyzed forms, Alternatively, it may be used in a hydrolyzed form in the following solvent. In particular, from the viewpoint of increasing the curing rate after coating, it is preferable to use the (partially) hydrolyzed form.
  • the molar ratio of water involved in the hydrolysis to the hydrolyzable group is in the range of 0.1 to LO.
  • hydrolysis a conventionally known method can be applied.
  • acids such as hydrochloric acid, acetic acid and maleic acid, sodium hydroxide
  • Amine compounds such as NaOH, ammonia, triethylamine, dibutylamine, hexylamine, octylamine, dibutylamine, etc., and salts of amine compounds, quaternary ammonia such as benzyl triethylamine, tetramethylammonium hydroxide, etc.
  • -Bases such as humic salts, fluorides such as potassium fluoride and sodium fluoride, solid acidic catalysts or solid basic catalysts (eg, ion exchange resin catalysts), iron-2-ethylhexoate , Titanium naphthate, dumbbell stearate, dibutinoletin diacetate and other organic metal salts of norevonic acid, tetrabutoxy titanium, tetra-i-propoxy titanium, dibutoxy (bis-2,4-pentanedionate) titanium, di i-propoxy (bis-1,4 pentanedionate) organic titanium esthetics such as titanium Organic zirconium esters such as zirconium, tetrabutoxyzirconium, tetrai-propoxyzinolecium, dibutoxy (bis 2,4 pentanedionate) zirconium and di i-propoxy (bis 2,4 pentanedionate) zirconium , Organometallic compounds such as
  • the addition amount of the catalyst is 0.01 to 10 parts by weight, preferably 0.1 to 1 part by weight, based on 100 parts by weight of the (partially) hydrolyzed compound. If this amount is less than 0.01 parts by weight, it may take too much time to complete the reaction or the reaction may not proceed. On the other hand, if it exceeds 10 parts by weight, it is disadvantageous in terms of cost, and the resulting composition or cured product may be colored or side reactions may increase.
  • the present composition can be used after diluted with a solvent.
  • the solvent include alcohols such as methanol, ethanol, propyl alcohol, isopropyl alcohol, ⁇ -butinoreanolol monole, isobutinoleanoreconole, sec butinorenoreconole, tert butinorenoreconole, diacetone alcohol, and the like.
  • Glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl enoate ether, propylene glycol monomethino ethenore, propylene glycol monoethyl ether, acetone, methyl ether
  • ketones such as ruketone, methyl isobutyl ketone and acetylacetone
  • esters such as ethyl acetate, butyl acetate and cetyl acetate, xylene and toluene.
  • the amount of solvent added is arbitrary. Considering the ease of painting, the ease of controlling the coating thickness, and the stability of the coating composition, the solvent content in the composition is 50-99. It is particularly preferred that the content is 70% by weight.
  • the coating material composition prepared as described above is applied to the surface of the base material to form a film, and this film is dried and cured to obtain a cured film having a low refractive index on the surface.
  • a formed coated product can be obtained.
  • the substrate on which the coating material composition is coated is not particularly limited, but examples thereof include inorganic substrates typified by glass, metal substrates, acrylic resin, polycarbonate, polyethylene terephthalate.
  • the organic base material represented by G. can be mentioned, and the shape of the base material can be a plate shape or a film shape. Furthermore, one or more layers may be formed on the surface of the substrate.
  • the method is not particularly limited.
  • Various ordinary coating methods such as curtain coating, knife coating, spin coating, table coating, sheet coating, single wafer coating, die coating, and bar coating can be selected.
  • the thickness of the cured film formed on the surface of the substrate can be appropriately selected according to the intended use and purpose, and is not particularly limited, but is preferably in the range of 50 to 150 nm.
  • the product of the refractive index and the film thickness of the cured film is the optical film thickness, and the optical film thickness of the cured film needs to be set to 1Z4 in order for the light of wavelength ⁇ to have the lowest reflectance. .
  • the thickness of the cured coating is preferably in the range of 50 to 150 nm.
  • the refractive index of the base material is 1.60 or less
  • a cured film having a refractive index of 1.60 or more is formed on the surface of this base material, and this is used as an intermediate layer. It is effective to form a cured film with the coating material composition according to the present invention.
  • the cured film for forming the intermediate layer can be formed using a known high refractive index material, and if the refractive index of the intermediate layer is 1.60 or more, the coating material composition according to the present invention Thus, the difference in refractive index from the cured film due to is increased, and an antireflection substrate excellent in antireflection performance can be obtained.
  • the intermediate layer may be formed of a plurality of layers having different refractive indexes.
  • anti-reflection applications include anti-reflection films, outermost surfaces of displays, automobile side mirrors, windshields, side glasses, rear glass inner surfaces, other vehicle glass, and building glass. .
  • the film formed from the coating material composition according to the present invention has high scratch resistance, antifouling property, chemical resistance, and crack resistance.
  • the performance can be maintained particularly well when the film is exposed to high temperatures during film formation or after film formation. For this reason, the film is coated on a plastic substrate such as a plastic substrate. Even in the case of forming a film, it is possible to form a film in which cracks are unlikely to occur during heating.
  • the silane compound represented by the following formula (1) is 47.8 parts (0.08 mole) of methanol and 32.4 parts of methanol, and 4.7 parts of ⁇ -glycidoxypropyltrimethoxysilane as an epoxy group-containing organic compound ( 0.02 mol) and Sarako 0.1 kg (0.1 mol ZL) of hydrochloric acid 36 parts were added to obtain a mixed solution.
  • This mixed solution was stirred in a thermostatic bath at 25 ° C. for 2 hours to obtain a silicone resin having a solid content of 10%.
  • propylene glycol monomethyl ether 93 5 parts was added and diluted to obtain a coating material composition having a solid content of 3%.
  • the silane compound represented by the above formula (1) 47.8 parts (0.08 mole) of methanol 317.1 parts is further added, and the epoxy group-containing organic compound is a siloxane oligomer represented by the following formula (2) 3.6 5 parts (0.01 mol) and 36 parts of 0.1N (0.1 mol ZL) aqueous hydrochloric acid were added to obtain a mixed solution.
  • This mixed solution was stirred for 2 hours in a thermostatic bath at 25 ° C. to obtain a silicone resin having a solid content of 10%.
  • 1028 parts of propylene glycol monomethyl ether was added and diluted to obtain a coating material composition having a solid content of 3%.
  • Hollow silica IPA (isopropanol) dispersion sol (solid content 20%, average primary particle size 60 nm, outer shell thickness about 10 nm, manufactured by Catalyst Kasei Co., Ltd.) is used as the hollow silica fine particles, and this is diluted with methanol to a solid content of 10% Thus, a dispersion sol was obtained. 10 parts of this dispersion sol and 90 parts of the silicone resin obtained in Example 2 are mixed, and 233.3 parts of propylene glycol monomethyl ether is mixed and diluted to obtain a coating material composition having a solid content of 3%. Obtained.
  • a coating material composition of 3% was obtained.
  • the surface was previously cleaned with a UV-ozone cleaner (excimer lamp “Model H0011” manufactured by Usio Electric Co., Ltd.).
  • a UV-ozone cleaner excimer lamp “Model H0011” manufactured by Usio Electric Co., Ltd.
  • coated with a wire bar coater to a film thickness of about lOOnm, and at 100 ° C
  • a cured coating was obtained by treatment for 30 minutes.
  • This cured film was subjected to the following evaluation tests for minimum reflectance, abrasion resistance, fingerprint removability, alkali resistance, and crack resistance.
  • the surface of the cured film is rubbed with an abrasion tester ("SHIDON Science Co., Ltd.” HEIDON-14DRJ, steel wool # 0000, load 9.8kPa (100gZcm 2 ) ").
  • the mechanical strength was determined according to the following evaluation criteria by observing the bell.
  • a fingerprint was attached to the surface of the cured coating, and the appearance after the fingerprint trace was wiped off with OA Tresy (manufactured by Toray Industries, Inc.) was observed, and the fingerprint removability was judged according to the following evaluation criteria.
  • the coated acrylic board is placed at 110 ° C for 30 minutes, then at 120 ° C for 30 minutes, then another 13
  • Firing was performed at 0 ° C for 30 minutes, and the crack resistance was evaluated at the firing temperature at which cracks occurred in the coating.
  • the present invention has a low refractive index and a high refractive index when the coating is formed or when exposed to a high temperature after the coating is formed.
  • the present invention can be applied to a coating material composition capable of maintaining scratch resistance, antifouling property, chemical resistance, and crack resistance, and a coated product in which a film is formed with this coating material composition.
  • a film having high antireflection properties, scratch resistance, antifouling properties, chemical resistance, and crack resistance can be formed, and these properties, particularly high crack resistance, can be formed. Can be maintained even when exposed to high temperatures.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Paints Or Removers (AREA)
  • Surface Treatment Of Optical Elements (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention décrit une composition de revêtement qui permet de former un film de revêtement pouvant maintenir un faible indice de réfraction, une forte résistance à l'abrasion, une bonne propriété d’anti-salissure, une forte résistance au produits chimiques et une forte résistance à la déchirure même lorsqu'il est formé sur un matériau de base en plastique tel que des bases faites en plastiques et est exposé à des températures élevées pendant ou après la formation du film de revêtement. L’invention décrit plus spécifiquement une composition de revêtement contenant un composé de type silane représenté par la formule générale (A) ci-dessous et un composé organique contenant des groupes époxy qui possède un ou plusieurs groupes époxy par molécule, la teneur en composé de type silane étant de 60 à 97 % en poids par rapport à la quantité totale des composants de la résine et la teneur en composé organique contenant des groupes époxy étant de 3 à 10 % en poids par rapport à la quantité totale des composants de la résine. XmR13- mSi-Y-SiR13- mXm (A) [dans la formule, R1 représente un groupe hydrocarboné monovalent ayant de 1 à 6 atomes de carbone ; Y représente un groupe organique bivalent ayant un ou plusieurs atomes de fluor ; X représente un groupe hydrolysable ; et m représente un nombre entier valant de 1 à 3.] Un film de revêtement fait à partir d'une telle composition de revêtement peut maintenir une forte résistance à la déchirure même lorsqu'il est exposé à des températures élevées.
PCT/JP2006/303767 2005-03-02 2006-02-28 Composition de revetement et article revetu WO2006093156A1 (fr)

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EP06714896A EP1854854A4 (fr) 2005-03-02 2006-02-28 Composition de revetement et article revetu
US11/816,832 US8273811B2 (en) 2005-03-02 2006-02-28 Coating material composite and coated article

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008115357A (ja) * 2006-11-06 2008-05-22 Far Eastern Textile Ltd 低反射フィルム生産用成膜溶液をゾル−ゲル法によって製造する方法及び該成膜溶液を用いた低反射フィルムの製造方法
JP2010180375A (ja) * 2009-02-09 2010-08-19 Shin-Etsu Chemical Co Ltd 光硬化型コーティング剤組成物、被膜形成方法及び被覆物品

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9353268B2 (en) * 2009-04-30 2016-05-31 Enki Technology, Inc. Anti-reflective and anti-soiling coatings for self-cleaning properties
US9376593B2 (en) 2009-04-30 2016-06-28 Enki Technology, Inc. Multi-layer coatings
KR101800743B1 (ko) * 2011-01-10 2017-11-24 삼성전자주식회사 지문 돋보임 방지 피막용 조성물, 상기 조성물을 이용한 지문 돋보임 방지 피막, 및 상기 피막을 포함하는 물품
US9109140B2 (en) 2013-01-22 2015-08-18 Xerox Corporation Mixed organosiloxane networks for tunable surface properties for blanket substrates for indirect printing methods
US9493676B2 (en) * 2013-03-19 2016-11-15 Xerox Corporation Formulation composition for fluorinated organosiloxane network
US9376589B2 (en) 2014-07-14 2016-06-28 Enki Technology, Inc. High gain durable anti-reflective coating with oblate voids
US9598586B2 (en) 2014-07-14 2017-03-21 Enki Technology, Inc. Coating materials and methods for enhanced reliability
US9382449B2 (en) 2014-09-19 2016-07-05 Enki Technology, Inc. Optical enhancing durable anti-reflective coating
PL3203273T3 (pl) * 2014-09-30 2022-03-14 Nippon Sheet Glass Company, Limited Płyta szklana powleczona nisko-odblaskowo, podłoże szklane oraz urządzenie do konwersji fotoelektrycznej
KR20220132328A (ko) * 2021-03-23 2022-09-30 삼성에스디아이 주식회사 경화형 수지 조성물, 이로부터 제조되는 박막, 및 상기 박막을 포함하는 색 변환 패널 및 표시 장치

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0625599A (ja) * 1992-07-10 1994-02-01 Asahi Optical Co Ltd スピンコート可能な反射防止組成物
JPH06347605A (ja) * 1993-06-04 1994-12-22 Asahi Optical Co Ltd コーティング組成物の製造方法
WO2005059051A1 (fr) * 2003-12-19 2005-06-30 Nissan Chemical Industries, Ltd. Pellicule d'enrobage presentant un indice de refraction faible et un grand angle de contact avec l'eau

Family Cites Families (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58222160A (ja) * 1982-06-16 1983-12-23 Tokuyama Soda Co Ltd コ−テイング用組成物
JPS5943070A (ja) 1982-09-02 1984-03-09 Seiko Epson Corp 硬化膜を有する複合体
JPS59115840A (ja) 1982-12-24 1984-07-04 旭硝子株式会社 低反射率塗膜
JPS60262833A (ja) 1984-06-11 1985-12-26 Tokuyama Soda Co Ltd 被覆合成樹脂材
JPS6110043A (ja) * 1984-06-26 1986-01-17 Asahi Glass Co Ltd 防汚性を有する低反射率ガラス
EP0186186B1 (fr) 1984-12-27 1991-07-24 Asahi Glass Company Ltd. Composition de résine durcissable
JPS61276832A (ja) 1985-05-31 1986-12-06 Nippon Sheet Glass Co Ltd 耐摩耗性のすぐれた被覆プラスチツク成形体の製造方法
JPH0778186B2 (ja) 1986-05-23 1995-08-23 旭硝子株式会社 硬化性組成物
JPS6424422A (en) 1987-07-20 1989-01-26 Sanyo Electric Co Formation of fine pattern
JP2629813B2 (ja) 1988-04-28 1997-07-16 旭硝子株式会社 低反射透明成形体
JP3155025B2 (ja) 1991-05-17 2001-04-09 旭硝子株式会社 表面処理された建築・建装用物品および該物品の製造方法
JPH04343366A (ja) 1991-05-20 1992-11-30 Asahi Glass Co Ltd 電子写真用キャリアの表面処理剤、およびそれで処理されたキャリア
JP2819371B2 (ja) 1992-03-27 1998-10-30 信越化学工業株式会社 室温硬化性オルガノポリシロキサン組成物及びその硬化物
JPH0629332A (ja) 1992-07-13 1994-02-04 Nec Corp 半導体素子吸着治具
JPH08311408A (ja) * 1995-03-15 1996-11-26 Seiko Epson Corp コーティング用組成物およびその製造方法および積層体
US6001163A (en) * 1997-04-17 1999-12-14 Sdc Coatings, Inc. Composition for providing an abrasion resistant coating on a substrate
US6348269B1 (en) * 1998-10-23 2002-02-19 Sdc Coatings, Inc. Composition for providing an abrasion resistant coating on a substrate having improved adhesion and improved resistance to crack formation
DE60035776T2 (de) 1999-04-23 2008-04-30 Sdc Coatings Inc., Anaheim Zusammensetzung für abriebfeste beschichtung
JP3657869B2 (ja) * 1999-10-29 2005-06-08 株式会社巴川製紙所 低反射部材
CN100478292C (zh) 2000-06-20 2009-04-15 日挥触媒化成株式会社 无机化合物颗粒及其制备方法
JP4126521B2 (ja) 2000-08-04 2008-07-30 信越化学工業株式会社 被膜形成用組成物用フロロオルガノポリシロキサン樹脂の製造方法
CN1283372C (zh) * 2001-04-02 2006-11-08 松下电器产业株式会社 疏水膜及其制造方法、使用该膜的喷墨头和喷墨式记录装置
JP4126545B2 (ja) * 2003-04-18 2008-07-30 信越化学工業株式会社 被覆物品並びに多層積層体

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0625599A (ja) * 1992-07-10 1994-02-01 Asahi Optical Co Ltd スピンコート可能な反射防止組成物
JPH06347605A (ja) * 1993-06-04 1994-12-22 Asahi Optical Co Ltd コーティング組成物の製造方法
WO2005059051A1 (fr) * 2003-12-19 2005-06-30 Nissan Chemical Industries, Ltd. Pellicule d'enrobage presentant un indice de refraction faible et un grand angle de contact avec l'eau

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP1854854A4 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008115357A (ja) * 2006-11-06 2008-05-22 Far Eastern Textile Ltd 低反射フィルム生産用成膜溶液をゾル−ゲル法によって製造する方法及び該成膜溶液を用いた低反射フィルムの製造方法
JP2010180375A (ja) * 2009-02-09 2010-08-19 Shin-Etsu Chemical Co Ltd 光硬化型コーティング剤組成物、被膜形成方法及び被覆物品
US8221878B2 (en) 2009-02-09 2012-07-17 Shin-Etsu Chemical Co., Ltd. Photocurable coating composition, film forming method, and coated article

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US8273811B2 (en) 2012-09-25
JPWO2006093156A1 (ja) 2008-08-07
EP1854854A4 (fr) 2010-08-04
KR100901544B1 (ko) 2009-06-08
EP1854854A1 (fr) 2007-11-14
US20090043025A1 (en) 2009-02-12
KR20070118597A (ko) 2007-12-17

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